Hydrocarbon conversion



, the polymerization of any olen the liquid acid polymerizing Patented Oct. 8, 1946 2,408,725 HYDROCARBON CONVERSION Arnold Belchetz, Kew Gardens, N. Y., assignor to The M.

W. Kellogg Com pany, Jersey City, N. J.,

a corporation of Delaware Application September 4,

15 Claims.A (Cl. 2604683.15)

This invention relates to an improved method for producing olefin polymers. More particularly, the invention -relates to an improvement in the method in which olefins are rst absorbed in a liquid acid polymerizing catalyst, and the extract is then heated to polymerize the absorbed olefms.

Olefm hydrocanbons may be absorbed at relatively low temperatures in a liquid acid polymeriZirlg catalyst such as sulfuric acid or hydro-fluoric acid, and the absorbed olefns may then be polymerized by heating the extract to a suitable polymerizing temperature.

The conditions under which olefin hydrocarbons are absorbed by the liquid acid pclymerizing catalyst depend upon the molecular weight of the olefin hydrocarbon and also upon the molecular structure thereof. For example, in the absorption or" butylenes in sulfuric acid it is found that isobutylene is absorbed to a substantial degree at temperatures which are too W to effect substantial absorption of the normal butylenes. The selectivity of the absorption of isobutylene is efiected also by the strength of the acid, the ratio of acid to butylenes and the time of contact.

The selective absorption of isobutylene from a mixture including normal butylenes is theL acidV process which has been used extensively for the manufacture of tertiary butyl alcohol or in the preparation of di-isobutylene for hydrogenation to iso-octane.

The invention will be described further by speciiic reference to a modification of the cold acid process, although it will be readily understood that the invention is not limited to such specific application -but includes within its scope hydrocarbon by successive absorption of the olefin hydrocarbon in the liquid acid catalyst and polymerization of the absorbed olefin by heating the extract. The cold acid polymerization of isobutylene is selected as the speciiic example of the application of the invention for the reason that it is an important step in the production of isooctane and is a valuable method for separating isobutylene from nor- -mal butylenes prior to subjecting the latter to dehydrogenation for the production of butadiene. It will be understood, however, that the invention is applicable also to the polymerization of olefins having a greater or less number of carbon, atoms than isobutylene and is applicable also to the polymerization of olen hydrocarbons other than iso-oleiins such as normal olefins and dioleiins. For example, the process is applicable t0 the polymerization of normal butenes or butadienes although these applications of the invention are at present less important than the polymerization of isobutylene.

In the further description of the Ainvention reference will be made to the use of sulfuric acid as catalyst. Itis to be the rate of absorption 1942, Serial No. 457,530

understood, however, that the invention is not limited to the use of this specific catalytic agent but includes the use of other liquid acid catalysts, such as hydrofluoric acid, which are capable of absorbing olefin hydrocarbons at temperatures below polymerizing temperatures and promoting polymerization of the absorbed olefins when the extract is heated to a suitable temperature,

In the selective absorption of isobutylene in sulfuric acid a mixture of gases containing isobutylene, normal butenes and any accompanying parain hydrocarbons is contacted with the sulfurie acid under conditions eiiective to produce the desired absorption of isobutylene by the acid. These conditions are selected, with respect to the use to which the polymers and the remaining normal butenes lare to be put, to produce a greater or lesser degree of absorption of normal butylenes along with the isobutylene. When the principal kpurpose of the process is to obtain di-isobutylene for hydrogenaticn to iso-,octane a greater degree of absorption of normal butylenes is tolerable than in an operation carried out for the primary purpose of producing normal butylenes, substan tially free oi isobutylene, as a source material for the production of butadiene. In operating the process as a preliminary step for the production of butadiene it is desirable to effect as complete as practicable a removal of isobutylene from the mixture by absorption while keeping the a= sorption of normal butylenes at a practical minimum.

The isobutylene-acid extract is separated from and the latter are the unabsorbed hydrocarbons, then transferred elsewhere for further use, such as in the production of butadiene. The extract is then treated to regenerate the acid. This may be done by heating the extract to a temperature suiiciently high to polymerize the absorbed olens or .by diluting the extract to a lower acid strength and heating the dilute extract to evolve the isobutylene or by diluting the extract to a still lower acid strength and heating the dilute extract to evolve tertiary butyl alcohol. In the methods involving dilution the acid necessarily must be reconcentrated for further use in the absorption step. Preferably, therefore, the extract is treated Without dilution to polymerize the olens and regenerate the acid at the strength required for the absorption step. Relatively concentrated sulfuric acid 63 and 67 per cent is preferred for selective absorption of isobutylene. At lower concentrations decreases, and the rate oi corrosion of steel equipment increases. At higher acid strengths the rate of absorption of normal butylenes increases.

The polymerization of the isobutylene absorbed in the extract presents serious diiculties in commercial operations because the corrosive eiect of the acid is greatly intensified when the extract having a strength between is heated to the temperatures necessary to effect polymerization of the absorbed isobutylene. Previous practice in the commercial cold acid polymerization of isobutylene involves heating the extract by passage thereof through externally heated coils consisting of copper or steel or lead. Heating coils made of steel or copper have a relatively short life due to the corrosive effect of the extract and require frequent replacement. -By using thick. Walled lead coils a somewhat longer useful life is attained, but thes also require replacement at a frequency-which, in vievv of the expense of the tubes, is undesirable.

In accordance with the present invention the isobutylene-acid extract is heated to the polymerizing temperature, without contact at the extract with the above-mentioned metal coil-s at the polymerizing temperature, by contacting the extract with a hot fluid whereby the extract is heated to a temperature sufficiently high to polymerize the absorbed isobutylene. Preferably, heating of the extract is effected by cont-acting the extract with a vaporized fluid which is condensed by contact with the extract, the sensible heat and heat of vaporization of the huid being suilicient to impart to the resulting mixture a temperature sufficiently high to polymerize the isobutylene. Preferably also polymerization of the isobutylene is eflected by contacting the extract with a vaporized fluid which is similar in boiling characteristics to isobutylene. For example, the polymerization of the absorbed isobutylene is effected advantageously 'by mixing the extract with vaporized butane, either isobutane or normal butane, the temperature of the butane and the proportions of the butane and extract being regulated to produce a liquid mixture of the but-ane and extract at the desired polymerizin'g temperature.

The use of normal butane or isobutane is especially advantageous because oi the relationship of the boiling points of these materials to theboiling point of isobutylene. Since it is preferable to effect polymerization of the isobutylene while maintaining the extract in a liquid condition, it is desirab e rto maintain the polymerization reaction zone at a pressure suiciently high to prevent vaporization of isobutylene. When using normal butane vas the heating iiuid the pressure whichis maintained on the reaction zone to prevent vaporizaticn oi isobutylene is sufficient to insure condensation of the vapor` ized normal butano lwhen it is mixed with the extract. When using vaporized-i-sobutane as the heating luid it is necessary only lto apply a slightly higher pressure on the reactionz-one to insure condensation of the isobutane and the release of the heat of vaporization thereof.

Normal butano and isobutane Vare preferred agents as heating ui'ds for polymerizing isobutylene because oi their relative inertness in the reaction and because of their relationship to the Iboiling characteristics of the isobutylene. It is evident, howeverythat if the sensible heat of the heating fluid is sufficient alone to produce the desired polymerizing temperature, any gas or vapor may be used which does not condense on being mixed with the extract, or any unvaporized liquid may be employed. It is evident, also, that for the polymerization of olein hydrocarbons other than isobutylene by means of a condensible heating fluid other heating fluids than the tanes having different boiling characteristics may be employed.

Ordinarily, low-boiling hydrocarbons vsuch as those having three, four or five carbon atoms per moleculeare preferred because ci the relationship of their boiling characteristics to the boiling characteristics of the isobutylene and because they are readily separable from the resulting polymers by fractionation. While the use of lower boiling or higher boiling materials is Within the scope of the invention, these are practical ordinarily for use in the polymerization of isobutylene only Iwhen the sensible heat of the heating iiuid is sufficient te heat the extract to the polymerizing temperature. Relatively low-boiling heating uids require the application of an excessively high pressure to maintain liquid phase conditions in the reaction zone, Whereas higher boiling materials require heating the heating iluid to an excessively high tempera ture to vaporize it at the pressure necessary in the reaction zone.

In the selection of a heating fluid those ma"- terials should be avoided which will produce undesirable by-products either by reaction with themselves or'with the isobutylene polymers or which react with the acid catalyst to deactivate it. Low-boiling saturated paraiiin hydrocarbons suoli as propane, the butanes and pentaries are advantageous heating fluids because of their relative inertness `in the reaction zone. However, the use of other low-boiling hydrocarbons which are more reactive is not necessarily precluded. For example, vaporized propylene, butylene-p,I and pentenes may lbe usedto supply the necessary heat to the mixture as they undergo polymerization in the reaction zone increase the yield of olefin polymers and amplify the supply of heat by the release of heat of their reaction. Isobutylene obviously is satisfactory since it forms a product indistinguishable from that formed by polymerizing the absorbed isobutylene. Normal butylenes and propylene are satisfactory if the products of their polymerization can be tolerated in the polymer product of the process.

When the process of this invention is employed to separate isobutylene from the fresh feed to a process for making butadiene the succeeding stages of the latter process may furnisii a hydrocarbon mixture Iwhich is suitable for use the heating fluid. After the treatment of a gasecus hydrocarbon mixture, consisting essentially of C4 hydrocarbons-and including iso-olei'ins and normal olens, in accordance with this process, to effect substantial removal of iso-olens the remaining unabsorbed hydrocarbon mixture ordinarily is then subjected to a further extraction treatment, for example with acetone, to separate olens from paraflins. The unabsorbed paraifins from such a treatment ordinarily consist of a mixture of butanes proportions of isobutane and norm-al butane which depend upon the character of the process in which the gas mixture is formed. If the original feed is obtained by a thermal cracking treatment of hydro-carbon oils the butano mixture is found to predominate in normal butane, whereas ir" a catalytic hydrocarbon oil cracking process is the source of the gas mixture the butane,; predominate in isobutane. In either case this mixture constitutes a useful heating fluid for use in the present process.

Ordinarily, the mixture of normal butano and isobutane remaining after the extraction of olens contains a trace of isobut'ylene and a few per cent of normal butylenes. The presence of these olens in the heating fluid is not objectionable, however, since they are polymerized along with thefisobutylene absorbed inthe acid polymerizing catalyst. The presence of the polymers of such olefins in the polymer product is unobjectionable if the polymer product is to be supplied as fresh feed to an alkylation process. If the polymeris to be hydrogenated to iso-octane the presence of a small proportion of normal butenes in the heating fluid is not objectionable for the reason that the high proportion of isobutylene in the reaction zone will result in cross polymerization yof the normal butylene with isobutylene, resulting inthe production of an. iso-octene which can be hydrogenated to an octane of high octane ,num-

ber.- Theuse of a gas mixture from this sourceas the heating fluid in this process is particularly advantageous if 'the gases are obtained originally fromga catalytic cracking process and if the polymer product is to be employed as fresh feed to an alkylation process since, as pointed out above, such a mixture predominates in isobutane.

While inthe above discussion of suitable heating fluids specific reference is made only to hydrocarbons, it is to be understood that the invention is not limited to the use of hydrocarbons as heating iiuids. Any suitable uid may be used which does not form undesired reaction products. Consequently, fluids other than hydrocarbons which meet this necessary requirement may be used, particularly those which may be mixed with the olefin-acid extract in a vaporized condition and which are condensed by contact with the extract at the reaction temperature and pressure. For examples of suitable heating fluids other than hydrocarbons reference lmay be made to the ethers, such as dimethyl ether and diethyl` ether, alkyl chlorides such as methyl chloride and ethyl chloride. The ethers are preferable because of their relative inertness under the polymerization reaction conditions.

The invention will be described further in connection with the specific application thereof to the polymerization Vof isobutyene. Inconnection with such further description reference will be made to the accompanying drawing which illustrates diagrammatically an assemblage of apparatus for carrying out the specific application of the invention to the polymerization of isobutylene. It is to be understood, however, that the invention is not limited by such specific reference to the polymerization of isobutylene or by the reference to a specific assemblage of apparatus 'since the 'principles of operation illustrated are applicable to the polymerization of other oleiins, including normal olens and diolefins, by means of other combinations of apparatus and operating steps and by means of liquid polymerizing catalysts and operating conditions other than those referred to specically. l Referring to the drawing, the polymerization reaction is carried out in reactor I which is an elongated lead lined, acid-brick lined cylindrical vessel adapted to withstand the application of substantial pressure. Preferably, reactor I is filled with some suitable acid resistant packing such as ceramic Raschig rings. The interior'of reactor I communicates at one end thereof with a lead lined mixing nozzle 2.

'The acid-isobutylene Vextract is supplied to the operation through line 3 which connects with mixing nozzle 2. Line 3 is provided with a pump 4 for introducing the extract into nozzle 2 against the pressure maintained in reactor I.

The heating fluid is introduced in the system through line 5 which is provided with a pump 6. Line 5` connects with an accumulator 1 from. which .the heating fluid is transferred to .mixing Ythe molar ratio of nozzle 2 by means cumulator I with mixing nozzle 2. Line 8 is provided with a pump 9 for introducingthe'heating fluid" into mixing nozzle 2 against the reaction pressure. Heating meansv I0 is provided in line 8 to heat the heating fluid to the desired temperature. Preferably, the heating fluid is heated at I0 yto a temperature sufficiently high to vaporize it under the pressure maintained in line 8 and reactor I.

'As stated above, preferred heating fluids for the polymerization of isobutylene in accordance with the present invention are isobutane and normal butano. The use of normal butane permits the maintenance of a slightly lower pressure in reactor I but, on the other hand, the use of isobutane requires only a slightly higher pressure and does not require heating to as high a temperature at I0 to vaporize it. Furthermore, if it is desired to employ the isobutylene polymer product as charging stock to an alkylation operation for the production of iso-octane, the use of isobutane as the heating fluid is advantageous since 'its presence in the polymer product does not require fractionation prior to charging the polymer to the alkyation process. In this specific example, therefore, isobutane is accumulated at 1 and charged into mixing nozzle 2 at the desired rate after having been vaporized at I0.

The amount of isobutane required for polymerizing each unit of isobutylene charged to thesystem in the` extract through line 3 increases as the concentration of isobutylene in the extract decreases. The molar ratio of HzSOi to (74H3 inthe extract may vary from 0.5:1'.0 to 4.0:l.0. It is preferable when extracting isobutylene in preparation for the polymerization step to maintain the concentration of isobutylene in the extract supplied through line 3 such that H2SO'4 to Cil-Is is within the range of 0.7:1 to 1.2:1.0. Higher molar ratio-s of acid to isobutylene increase the heat requirement of the polymerization step substantially and lower the selectivity of the extraction operation.

It is preferred ordinarily to maintain the polymerization zone at a temperature Within the range of .to 230 F. Lower temperatures may result in incomplete regeneration of the acid. The use of higher temperatures involves the danger of decomposing the acid. Within the range of temperatures given above the preferred range is F. to 210 F. Within this preferred range the higher temperatures apparently favor rapid polymerization with the formation of a high proportion of isobutylene dimers.

`The use of isobutane as the heating fluid requires the application of pressure on the polymerization reactor suiicient to prevent vaporization of isobutane at the reaction temperature. The vapor pressure of isobutane at 170 F. is 170 pounds per square inch (gauge) ,whereas at 210 F. it is 275 pounds per square inch (gauge). When using isobutane as the heating fluid the vapor pressure of this material at the reaction temperature selected represents the minimum pressure `at which it is advisable to operate the polymerizing reactor. butane as the heating fluid somewhat lower pressures may be employed, these being governed by .the vapor pressure of isobutylene at the reaction temperature. The vapor pressure of isobutylene at 170 F. is 160 pounds per square inch (gauge) whereas at 210 F. itis 255 pounds per square inch (gauge). The vapor pressure of isobutylene 75 at the selectedY reaction v,terilpereiilre is the of line 8 which connects ac- When employing normalv 2,4osg725 mum pressure at which it is. advisable to operate .the reactor when employing as .theheating fluid nor-mal butane or `.any other material-havinga Vapor pressure lower than that of isobutylene. The vapor pressure of the isobutane, or isobutylene, at the reaction temperature is higher than the Vapor-pressure of the reaction mixture, because of .the presence therein of lower boiling materials, such as polymers and normal butane. However, the vapor pressure of the isobutane-or isobutylene may be taken as a satisfactory minimumfor thepressure in the reactor. Preferably, the pressure on the reactor should be maintained somewhat above the indicated minimum. For example, when using isobutane as Ythe heating lluid the operating pressure at 170 F. should be about 200 pounds per square inch (gauge), wherefas at 210 l-T'. it should be about 300 pounds per square inch (gauge) As pointed out above, the heat required to polymerize a given quantity of isobutylene is greater when the concentration of isobutylene in the extract is relativelylow. The amount of isobutane, or other heating fluid, which must be injected into mixing nozzle 2 is aiected also by the temperature of the extract flowing through line 3, .the polymerizing `temperature selected and the temperature of the vap-orized heating iuid introduced into mixing nozzle 2.

The latent heat of condensation of isobutane Varies from 112 B. t. u. per pound of isobutane at `a pressure of 200 pounds per square inch (gauge) to 118 B. t. u. per pound of-isobutane at a pressure of 300 pounds per square inch (gauge). Additional heat may be made available to the reaction zone from the isobutane by superheating the isobutane vapors or by cooling the liquid isobutane from its boiling point to the reaction temperature. The vari-ation in the quantity of isobutane required for various operating conditions and various-concentrations of isobutylene in the extract When the extract owing through line 3 is supplied to mixing nozzle V2 at 95 F. and when the Vaporized isobutane is supplied to the `mixing nozzle 2 through line 8 at a temperature of 300 F.

may be summarized in the following'table:

The Vaporized isobutane and extract are intimately mixed by suitable contact means in mixing `nozzle 2 whereby the isobutane is condensed and the resulting mixture is brought to the preselected reaction temperature. The reaction mixture then flows through the elongated reactor l at va rate which providesthe holding time necessary to effect substantially complete polymerization of .the isobutylene. Necessarily, the holding time in reactor I will be governed by vthe polymerizing temperature since this reaction proceeds at higher rates, the higher the'temperature. Within the range of conditions set forth above a holding time of minutes ordinarily will be the maximum time required, and a holding time of 3 to 5 minutes ordinarily is found to be preferable.

The temperature of the reaction mixture owing through the reactor varies but littlefrom the initial temperature assumed bythe reaction mix- .ture formed by the rapid and-intimate mixing ofthe isobutane and extract. The form-ation of polymers-from the tertiary butylaloohol and tertiary butyl esters, which are the forms in which the isobutylene is retained in the extract, occurs through reactions which are endothermic. It would beexpected, therefore, that the occurrence of such reactions :in the mixture as the latter flows through the elongated reaction zone would lower the temperature of the reaction `mixture progressively along the path of iiow of the reactants. However, the initial heating ofthe extract by admixture thereof with the Vaporized isobutylene results in the regeneration of isobutylene as such from the extract. The reactions by which such regeneration-occurs also are endothermic, so that a portionof the heat supplied at the point `of mixing of rthe isobutylene and ex- .tract is absorbed bythe endothermic reactions resulting in the release of isobutylene. However, isobutylene thus released polymerizes to di-isobutylene during the passage #of-.the reaction mixture through the reaction zone. This reaction-is highly exothermic and serveswto supply the heat which is absorbed by the reactions by which diisobutylene is produced directly from the tertiary butyl alcohol and tertiary butyl esters contained in the extract. Consequently, once the reaction mixture is heated to the desired reaction temperature by the cooling and condensation of the vaporized isobutane the reactions resulting in the formation of nii-isobutylene `apparently do not absorb or generate sufcient heat to affect materially the temperature of the reaction mixture. In the preparation ofv cli-.isobutylene for hydrogenation to iso-octane it is desirable, for obvious reasons, to operate under conditions which promote the formation of dimers and minimize the formation of trimers. It is found also that dimers are preferable to trimers in a polymer feed for an alkylation operation process `since the consumption of acid `in the alkylation process is lower when alkylating dimers than when alkylating trimers. It is desirable, therefore, to heat the reaction mixture rapidly `to a relatively high polymer-ming temperature, limit the holding time at the polymerizing temperature to that necessary to effect maximum formation of Vdi-isobutylene, and then'quickly lower the temperature of the reaction mixtureto the point `at which polymerization -is substantially inhibited.

`When operating in this manner it is'desirable that the reaction mixture emergingY from reactor l be cooled rapidly to a temperatureV at which polymerization is substantially inhibited. Slow cooling maintains the mixture for an vexcessive period of time in the relatively low range of polymerizing temperatures at which formation of trimers is favored. Such rapid 'cooling of the reaction mixtureY may be accomplished'byany suitable means. It is preferred, however, in this process to eifect'such rapid cooling by 'quenching with a 'cooling iiuid the 'reaction' mixture emerging from reactor I to a temperature suiii'ciently low to minimize corrosion in equipment through which the mixture passes subsequently. Any suitable'iluid may be used for this purpose, the requirements of such a fiui'dibe'ing substantially the same as those set forth 'above for the heating iiuid except that materials which would be less desirable Aas heating Yiuids because of their 'reactivity at the-highertemperatures-may be used to quench the reaction mixture. Conveniently, the same fluid employed "for heating 4purposes also may be employed as the quench. -In the specific example illustrated -i'n the drawing Ya portion of the Visrib'utane supplied through line 8 `ature prior to the use For rapidand intimate mixing of the reaction Aiently takes the and an upper is diverted therefrom through line II. Cooling means I2 may be provided in line II if desired to chill the isobutane to a still lower temperthereof as the quench.

mixture and the quench iiuid a mixing nozzle I3, which is preferably lead lined and may bev similar in construction to mixing nozzle 2, is provided at the exit of reactor I. Line II connects with mixing nozzle I3 in order to supply the liquid isobutane for quenching the hot reaction mixture as it emerges from reactor I. A suincient quantity of the cooling fluid is preferably supplied through line II so that the resulting mixture thereof with the reaction products will have a temperature of from 120 to 150 F.

The quenched mixture in mixing nozzle I3 is withdrawn therefrom through line I4 which connects with a cooler I5 for cooling the mixture to a still lower temperature. Cooler I5 convenform of a coil I6 maintained in indirect heat exchange with cooling water.

The mixture passing through coil I6 is cooled preferably to a temperature of about 100 F. `and emerges therefrom into line I1 which connects coil I6 with a settler I8. Settler `I8 may be operated at the same pressure as cooler I5 and reactor I, but if a lower pressure is desired a valve I9 may be provided in line I1 for the necessary release of pressure.

In settler I8 the mixture of polymer and acid is permitted to separate into a lower acid layer hydrocarbon layer. The regenerated acid constituting the acid layer is withdrawn from settler I8 through line 20 for return to the olefin extraction operation. The hydrocarbon layer including polymers and isobutane is withdrawn from settler I8 through line ZI which connects with neutralizer 22. In order to neutralize the acid content of the hydrocarbon mixturev flowing through line 2l alkali is introduced into the mixture through line 23 which connects with line 2|. The hydrocarbons and alkali are intimately mixed by passage thereof through mixing nozzle 24, and the resulting mixture is then permitted to separate The alkali separa-tes as a lower phase and is withdrawn through line 25. If desir d a portion of this material may be recirculated through line 2E which connects line 25 with line 23. Theneutralized hydrocarbon mixture which separates in neutralizer 22 as an upper layer is withdrawn therefrom through line 21 which connects with fractionator 28.

The hydrocarbon mixture may be preheated as desired by heating means 29 located in line 21 prior to its introduction thereof into fractionator 28. In fractionator 28 the hydrocarbon mixture is subjected to fractionating conditions adapted to separate overhead the isobutane employed as the heating and quenching fluids as ywell as accompanying materials of similar boiling characteristics such as unconverted isobutylene. This material passes overhead from fractionator 28 through line 30 which is provided with condensing means 3| and which connects with accumulator 32. From accumulator 32 the condensate is withdrawn through line 33 provided with pump 34. Line 33 connects with accumulator 1 whereby material flowing therethrough 'is returned forreuse as heating or quenching fluid. Av portion of thek condensate-flowing through line 33 may be diverted to line 35 and returnedy to the ,upper portion of fractionator .28 as reiiux.

The polymer product of the process is withdrawn from the lower portion of fractionator 28 through line 36 for further handling. This material may be used directly as an ingredient of motor fuel but preferably is hydrogenated prior to such use. This material also may be employed as feed stock for an alkylation process.

If the polymer product is to be employed in an alkylation process and if isobutane is employed as the heating and quenching fluid in the polymerization process it may be desirable to eliminate the fractionation step carried out at 28. All or a portion of the material flowing through line 21 may be diverted therefrom throughline 31 for passage directly to an alkylation reactor. Cooling means 38 may be provided in line 31 to reduce the temperature of this material to that of the alkylation reactor. When operating in this manner the isobutane required for heating and quenching in the polymerization process may be recovered from the alkylation process as a portion of the isobutane normally recycled in that process.

1. In the method of converting olefin hydrocarbone in which olefin hydrocarbons are absorbed in an acid polymerizing catalyst at temperatures below polymerizing temperatures and the extract thus obtained is heated under pressure to a temperature sufficiently high to polymerize the absorbed ole'ns in the liquid phase, the improvement which comprises mixing said extract while at a temperature below polymerizing temperatures and at the polymerizing pressure with hydrocarbon vapors comprising at least a substantial proportion of an isoparaffin hydrocarbon boiling above the polymerizing temperature at the polymerizing pressure in proportions which produce a resulting mixture of extract and condensed vapors which is at the desired polymerizing temperature, separating from the resulting polymerized product regenerated acid catalyst and a hydrocarbon mixture comprising the polymers and the isoparafn hydrocarbon, recycling said regenerated acid catalyst to said absorption step, and subjecting said hydrocarbon mixture comprising olefin polymers andthe iso-paraffin hydrocarbon to alkylation reaction conditions.

2. In the method of converting relatively low boiling oleiin hydrocarbons in which such low boiling olens are absorbed in an acid polymer- .f

Ysubstantially lower than saidabsorbed olefinsin proportions which produce a resulting mixture of extract and condensed vapors which is at the desired polymerizing temperature, maintaining the pressure on the mixture undergoing polymerization sufliciently high to maintain said oleiins and condensed vapors substantially Kcompletely in a liquid condition, separating from the resulting polymerized product regenerated acid catalyst and a hydrocarbon mixture comprising olefin polymers and said isoparaflin hydrocarbon, recycling said regenerated acid catalyst to said'absorption step, and subjecting said hydrocarbon mixture comprising oleiin polymers and said isoparaflin hydrocarbon to alkylation reaction conditions..

3.' In the method of converting butene in which butene is absorbed in an acid. polymerizing catalyst at'temperatures below polymerizing temperatures and the extract thus obtained is heated under pressure to a temperature suinciently'high to `polymerize the absorbed butene in the liquid phase, the improvement which comprises mixing saiotextract while at a temperature below polymer-izing temperatures and at the polymerizing pressure with hydrocarbon vapors comprising at least a substantial proportion of isobutane in proportions which. produce` a resulting; mixture of extract and condensed hydrocarbons which is at theadesired` polymerizing temperature, separating from the-resulting, polymerized product regenerated acid catalyst and a hydrocarbon mixture comprising butene polymers and isobutane, recycling said regenerated acid catalyst to said absorption step, and subjecting said hydrocarbon mixture comprising isobutane and butene polymers to alkylation reaction conditions.

42 In the methodof converting butenein which butene is absorbed in an acid polymerizing catalystat temperaturesxbelow polymerizing temperatures and the extract thus obtained is heated under pressure to a. temperature sufficiently high to polymerize the absorbedv :butenel in the liquid phase, the improvement which comprises mixing said'extract while at a temperature below polymerizing temperatures and at the polymerizing pressure with isobutane vapors in proportions which produce aresulting mixture of extract and condensediisobutanewhich is atthe desired polymerizing temperature, separating from the resulting polymerized product., regenerated acid catalyst and a mixture of butene polymers and isobutane, recycling said'l regenerated acid` catalyst to said absorptionv step, and subjecting saidmixture of 'butene polymers and isobutane to alkylation reaction conditions.

5. In the method of converting butene in which butene is absorbed Vin an acid polymerizing catalyst-at temperaturesY below polymerizing temperatures and the extract thus obtained is heated under pressure to a temperature sufficiently high to polymerize the absorbed butene in the liquid phase, the improvement which comprises mixing said extractV while at a temperature belowpolymerizing temperatures and at the polymerizing pressure with hydrocarbon vapors comprising at least a substantial proportion of isobutane in proportions which produce a resultingmixtureof extract and' condensed hydrocarbons which is at the desired polymerizing temperature, permitting the mixture to remain at thel polymerizing temperature for a time su'cient to effect the desired polymerization of butene, then admixing the reaction mixture with a suicient quantity of relatively cold liquid hydrocarbons comprising at least a substantial proportion-of`isobutane to reduce the temperature of the mixture from the polymerizing temperature to a non-polymerizing temperature, separating from the resulting polymer'- ized product regenerated acid rcatalyst and a hydrocarbon mixture comprising butene polymers andV isobutane, recycling said regenerated acid catalyst to said absorption step, and subjecting said hydrocarbon mixture of isobutane and butene polymers to alkylation reaction conditions.

6. Inthe method of converting olefin hydrocarbonel in which olen hydcarbons are absorbed inan acid-polymerizing catalyst at temperatures below polymerizing temperatures and the extract thus obtained is heated under pressure to a temperature sumciently high to polymerize the absorbed oleiins in the liquid phase, the-improvement which comprises mixing said-extractv while at a temperature below polymerizing tempera-- tures and at the polymerizing pressure with vapors of an isoparafn hydrocarbon boiling above the polymerizing temperature at the polymerizing` pressure in proportionsl which produce a resultingmixture of extract and condensed isoparafn hy'- drocarbons which is at the desired polymerizingtemperature, permitting the mixture to remainat the polymerizing temperature-for a-time sufncient to effect the desired polymerization' and regen-- erate the polymerizing catalyst, thereafter separating the resulting mixture of isoparain hydro.- carbons and olefin'polymers from the accompanying acid catalyst, recycling acid catalyst thus separated to said absorption step, and subjecting' the said hydrocarbon mixtureof isoparamn hydrocarbons andolen polymers to alkylation reaction conditions.

7. The method of treating a hydrocarbonmixture comprising normal oleiinsand iso-olens which` comprises contacting said mixture with an acid polymerizing catalyst at temperatures below polymerizing` temperatures and sufficiently low to absorb a portion onlyof said olen hydrocarbons predominating in iso-olens, separating the resulting extract from unabsorbed hydrocarbons, mixing with said extract whileat a temperature below polymerizing temperatures and at the polymerizing pressure with vapors of an isoparaiiin hydrocarbon boiling above the polymerizing temperature atV the polymerizing pressure in proportions which produce a resulting mixture-of extract and condensed isoparaln vaporswhich is at the desired polymerizing temperature, maintaining the mixture at the polymerizing temperature-for a time sufdcient to effect polymerization of the olefin hydrocarbons and regeneration of the acid catalyst, thereafter separating from the acid catalyst a mixture of olefin-polymers and isoparafin hydrocarbons, recyclingv said separated acid catalyst to said absorption step, and subjecting said mixture of olenD polymers and isoparaidnr hydrocarbons toalky-lation reaction conditions.

8. A method'for treating a-low` boiling hydrocarbon mixture comprising normal butylenes and isobutylene which comprises contacting saidmixture with an acid polymerizing catalyst at temperatures suiciently low to avoid polymerization and eiect absorptionv of aV portion only of said butylenes predominatingy in isobutylene, separating the extract thusv obtained from` unabsorbed hydrocarbons, mixing the extract while at a temperature below polymerizing temperature andkv at the polymerizing pressure with butane vapors comprisingr atk least a substantial proportion of isobutane in proportions which produce a resulting mixture of extract and condensed vapors which is at the desired polymerizing temperature, separating from the resulting polymerized product amixture of butylene polymers and isobutane and regenerated acid catalyst, recycling said regenerated acid catalyst to said absorption step, and subjecting saidv mixture comprising butylene polymers and isobutane to alkylation reaction conditions.

9. A method for treating a low boiling hydrocarbon mixture comprising normal butylenes and isobutylene which comprises contacting said mix'- ture with an acid polymerizing catalyst at temperatures suiiciently low to avoid polymerization and eiect absorption of a portion only of said butylenes predominating in isobutylene, separating the extract thusobtained from unabsorbed hydrocarbons, mixing the extract while ata temperature below polymerizing temperature and at the polymerizing pressure with butane vapors comprising at least a substantial proportion of isobutane in proportions which produce a, resulting mixture of extract and condensed vapors which is at the desired polymerizing temperature, maintaining the mixture at the polymerizing temperature for a time sulicient to eiect substantially complete polymerization of the absorbed butylene and regeneration of the acid catalyst, then admixing with the reaction mixture a sufcient quantity of cold liquid butane comprising at least a substantial proportion of isobutane to reduce the temperature of the mixture to a non-polymerizing temperature, separating a hydrocarbon mixture comprising isobutane and butylene polymers and regenerated acid catalyst, recycling said regenerated acid catalyst to said absorption step, and subjecting said hydrocarbon mixture comprising isobutane and butylene polymers to alkylation reaction conditions.

10. A method for treating a low boiling hydrocarbon mixture comprising normal butylenes and isobutylene which comprises contacting said mixture with a sulphuric acid polymerizing catalyst at 'temperatures sufciently low to avoid polymerization and effect absorption of a portion only of said butylenes predominating in isobutylene, separating the extract thus obtained from unabsorbedhydrocarbons, mixing the extract while at a temperature below polymerizing temperature and at the polymerizing pressure with butane vapors comprising at least a substantial proportion of isobutane in proportions which produce a resulting mixture of extract and condensed vapors which is at the desired polymerizing temperature, maintaining the mixture at the polymerizing temperature for a time suicient to effect substantially complete polymeri'zation of the absorbed butylene and regeneration of the sulphuric acid catalyst, then admixing with the reaction mixture `a suftcient quantity of least a substantial proportion of isobutane to reduce the temperature of the mixture to a nonpolymerizing temperature, separating a hydrocarbon mixture comprising isobutane and butylene polymers and regenerated sulphuric acid catalyst, recycling said regenerated sulphuric acid catalyst to said absorption step, and subjecting said hydrocarbon mixture comprising isobutane and .butylene polymers to alkylation reaction conditions. k

l1. In the method of converting butene in which butene is absorbed in an acid polymerizing catalyst at temperatures below polymerizing temperatures and the extract thus obtained is heated under pressure to a temperature sufficiently high to polymerize the absorbed butene in the liquid phase, the improvement which comprises mixing said extractv while at a temperature below polymerizing temperatures and at the polymerizing pressure with isobutane vapors in proportions which produce a resulting mixture of extract and condensed isobutane whichis at the desired polymerizing temperature, separating. from the resulting polymerized product regenerated acid catalyst and a mixture of butene polymers and isobutane, recycling'said regenerated acid catacold liquid butane comprising at lyst to said absorption step, subjecting said mixture of butene polymers and isobutane to alkylation reaction conditions, recovering unreacted isobutane from the alkylation reaction, and recycling said unreacted isobutane to said polymerization step.

12. A method for processing a hydrocarbon gas produced by cracking treatment of hydrocarbon oil and containing isobutylene, normal butylene, and isobutane, which comprises absorb-ing the isobutylene content of said gas in an acid polymerizing catalyst at temperature below polymerizing temperature, treating unabsorbed gas to separate normal butene therefrom whereby a relatively paraflinic residual fraction containing isobutane is produced, vaporizing at least a portion of said residual isobutane fraction at a pressure effective for polymerizing said isobutylene, mixing the isobutylene extract while at a temperature below polymerizing temperatures and at the polymerizing pressure with said vaporized isobutane fraction in proportions which produce a resulting liquid mixture which is at the desired polymerizing temperature, separating from the resulting polymerized product regenerated acid catalyst and a mixture of butene polymers and isobutane, recycling said regenerated acid catalyst to said absorption step, and subjecting said mixture lof butene polymers and isobutane to alkylation reaction conditions. 13. .In a process of producing higher boilin hydrocarbons vfrom isobutane and isobutylene wherein an absorption product of isobutylene in sulfuric acid is heated to polymerize at least a part of said isobutylene and polymers thus formed are reacted with isobutane in the presence of an alkylation catalyst, the improvement which comprises adding isobutane in the vapor phase under a pressure high enough to condense isobutane and supply heat for said polymeriza-v tion and to produce substantially dry isobutane and feeding resulting polymer and substantially dry isobutane to the alkylation unit. y

14. A process of producing higher boiling hydrocarbons from isobutane'and an olen which comprises adding isobutane in the vapor phase to an absorption product of said olen in sulfuric acid under a pressure between about the vapor pressure of isobutane at F. and about 300 pounds per square inch at which isobutane'condenses and supplies heat for polymerization of said absorbed oleiin and substantially dry isobutane isproduced and contacting resulting polymer and substantially dry isobutane with an alkylation catalyst under alkylating conditions.

15. In a, process of producing higher boiling hydrocarbons from isobutane and an olen wherein an absorption product of said olefin in an inorganic acid of polymerization strength is heated to polymerize at least a part of the olen content and polymersY thus formed are reacted with isobutane in the presence of an alkylation catalyst, the improvement which comprisesvadding. isobutane in the vapor phase under a pressure high enough to condense isobutane and supply heatfor said polymerization andk to produce substantially dry isobutane and feeding resulting polymer and'substantially dry isobutane to the aikyiaucn unit.

' ARNOLD BELCHETZ. 

